Deodorant compositions

ABSTRACT

This invention relates to deodorant compositions containing polytrimethylene ether glycol homo- and copolymers and/or polytrimethylene glycol ester(s) in a variety of physical forms. In at least one embodiment, the polytrimethylene ether glycol homo- and copolymers and/or polytrimethylene glycol ester(s) are derived predominantly from monomers (e.g., 1,3-propanediol) obtained from renewable resources, and are thus more environmentally friendly in terms of manufacture, use and disposal.

FIELD OF THE INVENTION

This invention relates to deodorant compositions containingpolytrimethylene ether glycol homo- and copolymers and/orpolytrimethylene glycol ester(s) in a variety of physical forms. In atleast one embodiment, the polytrimethylene ether glycol homo- andcopolymers and/or polytrimethylene glycol ester(s) are derivedpredominantly from monomers (e.g., 1,3-propanediol) obtained fromrenewable resources, and are thus more environmentally friendly in termsof manufacture, use and disposal.

BACKGROUND

There are a large number of deodorant products available, most of whichare in the form of solid sticks, sprays, solutions, creams, ointments,lotions, gels or emulsions. The ingredients in the formulated productsin general serve as emollients, humectants, moisturizers, emulsifiers,lubricants, antimicrobials, cosmetics, fragrances, rheology modifiers,etc. Some of the products are solvent-based and others are water-based.

Most often deodorant products contain an active ingredient incorporatedin a delivery vehicle. The desired effect of a deodorant product isachieved either by the deodorant active ingredients or by the vehicleitself at the site of application, in most cases on the skin.

The major types of deodorant vehicles most frequently fall into thefollowing categories: (a) solutions; (b) emulsions, both oil-in-waterand water-in-oil, including, for example lotions and creams); (c)suspensions; (d) gels; and (e) solids (including semi-solids) including(for example) stick products. An extensive discussion of personal careand cosmetic vehicles is found in Handbook of Cosmetic Science andTechnology, Second Edition, edited by M Paye, A. O. Barel and H. I.Maibach, pages 99-123 (2005).

The majority of ingredients used in deodorant products, includingpolyols and silicones, are synthetic and are derived from petrochemicalsources. The recent trend of the industry is to provide products toconsumers that are natural and reduced in petroleum-based productcontent.

Co-owned U.S. application Ser. No. 11/801,872, filed May 11, 2007,entitled “PERSONAL CARE COMPOSITIONS”, discloses a personal carecomposition comprising an effective amount of at least one activepersonal care ingredient in a vehicle, wherein the vehicle comprisesfrom about 0.1 to 100% by weight, based on the weight of the vehicle, ofpolytrimethylene ether glycol. Specific molecular weight ranges forpolytrimethylene ether glycol are not disclosed, and preferred amountsof polytrimethylene ether glycol are 50 weight percent or less.

Certain mono- and diesters of polytrimethylene ether glycol (“PO3Gesters”) have properties that make them useful in a variety of fields,as disclosed in commonly owned U.S. application Ser. No. 11/593,954,filed Nov. 7, 2006, entitled “POLYTRIMETHYLENE ETHER GLYCOL ESTERS”.

US Patent Publication 2006/0165623 A1 describes a natural deodorantsystem and a natural system for topical and systemic delivery of activeingredients.

U.S. Pat. No. 5,650,143 discloses a deodorant cosmetic stick productwhich has a translucent or transparent light transmitting appearance,and a content of ingredients such as propylene glyol, sodium stearate,dimethicone copolyol, Triclosan, Pentadoxynol-200, and water.

US Patent Publication 2004/0241200 A1 describes personal care products,including deodorants, not containing tetramer and/or pentamercyclomethicone fluids, but including at least one neopentyl polyolpolyester derived from neopentyl glycol, at least one isoparaffin, and apersonal care formulation.

There is a need for products having reduced environmental impact. Thereis also an environmental advantage for manufacturers to provide productsderived from renewable sources. There thus exists a need for deodorantproducts comprising ingredients not derived from petroleum but fromrenewable resources. In addition, there is a need for ingredients andproducts that are environmentally friendly in respect to theirmanufacturing processes, their uses and their disposal.

SUMMARY OF THE INVENTION

One aspect of the present invention is a deodorant compositioncomprising an effective amount of at least one active deodorantingredient in a vehicle, wherein the vehicle comprises polytrimethyleneether glycol.

Another aspect of the present invention is a deodorant compositioncomprising a polytrimethylene ether glycol ester and at least one activedeodorant ingredient.

Another aspect of the present invention is a deodorant compositioncomprising an effective amount of at least one active deodorantingredient in a vehicle, wherein the vehicle comprises polytrimethyleneether glycol ester(s).

Another aspect of the present invention is a deodorant compositioncomprising an effective amount of at least one active deodorantingredient in a vehicle, wherein the vehicle comprises from about 5 to85 percent by weight, based on the weight of the vehicle, ofpolytrimethylene ether glycol.

In some preferred embodiments, the deodorant compositions comprisegreater than about 70 percent renewably sourced ingredients, based onthe total weight of the composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

All publications, patent applications, patents and other referencesmentioned herein, if not otherwise indicated, are incorporated byreference herein for all purposes as if fully set forth.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. In case of conflict, thepresent specification, including definitions, will control.

Except where expressly noted, trademarks are shown in upper case.

Unless stated otherwise, all percentages, parts, ratios, etc., are byweight.

When an amount, concentration, or other value or parameter is given aseither a range, preferred range or a list of upper preferable values andlower preferable values, this is to be understood as specificallydisclosing all ranges formed from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range. It is not intended that the scope of the invention be limitedto the specific values recited when defining a range.

When the term “about” is used in describing a value or an end-point of arange, the disclosure should be understood to include the specific valueor end-point referred to.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Use of “a” or “an” are employed to describe elements and components ofthe invention. This is done merely for convenience and to give a generalsense of the invention. This description should be read to include oneor at least one and the singular also includes the plural unless it isobvious that it is meant otherwise.

The materials, methods, and examples herein are illustrative only and,except as specifically stated, are not intended to be limiting. Althoughmethods and materials similar or equivalent to those described hereincan be used in the practice or testing of the present invention,suitable methods and materials are described herein.

Polytrimethylene Ether Glycol (PO3G)

The deodorant compositions of the invention generally include from about10 to about 90 wt % by weight of polytrimethylene ether glycol based onthe weight of the deodorant composition. In certain preferredembodiments, the compositions preferably include from about 10 to about85% by weight, and still more preferably from about 10 to about 70% byweight, of polytrimethylene ether glycol based on the weight of thedeodorant composition.

Polytrimethylene ether glycols are oligomers and polymers in which atleast 50% of the repeating units are trimethylene ether units. Morepreferably from about 75% to 100%, still more preferably from about 90%to 100%, and even more preferably from about 99% to 100%, of therepeating units are trimethylene ether units.

Polytrimethylene ether glycols are preferably prepared bypolycondensation of monomers comprising 1,3-propanediol, thus resultingin polymers or copolymers containing —(CH₂CH₂CH₂O)— linkage (e.g,trimethylene ether repeating units). As indicated above, at least 50% ofthe repeating units are trimethylene ether units.

In addition to the trimethylene ether units, lesser amounts of otherunits, such as other polyalkylene ether repeating units, may be presentalso. In the context of this disclosure, the term “polytrimethyleneether glycol” encompasses polytrimethylene ether glycol made fromessentially pure 1,3-propanediol, as well as those oligomers andpolymers (including those described below) containing up to about 50% byweight of comonomers.

The 1,3-propanediol employed for preparing the polytrimethylene etherglycols may be obtained by any of the various well known chemical routesor by biochemical transformation routes. Most preferably, the1,3-propanediol is obtained biochemically from a renewable source(“biologically-derived” 1,3-propanediol).

The most preferred source of 1,3-propanediol is via a fermentationprocess using a renewable biological source. As an illustrative exampleof a starting material from a renewable source, biochemical routes to1,3-propanediol (PDO) have been described that utilize feedstocksproduced from biological and renewable resources such as corn feedstock. For example, bacterial strains able to convert glycerol into1,3-propanediol are found in the species Klebsiella, Citrobacter,Clostridium, and Lactobacillus. The technique is disclosed in severalpatents, including U.S. Pat. No. 5,633,362, U.S. Pat. No. 5,686,276 andU.S. Pat. No. 5,821,092 (the disclosures of which are incorporated byreference herein for all purposes as if fully set forth). For example,U.S. Pat. No. 5,821,092 discloses, inter alia, a process for thebiological production of 1,3-propanediol from glycerol using recombinantorganisms. The process incorporates E. coli bacteria, transformed with aheterologous pdu diol dehydratase gene, having specificity for1,2-propanediol. The transformed E. coli is grown in the presence ofglycerol as a carbon source and 1,3-propanediol is isolated from thegrowth media. Since both bacteria and yeasts can convert glucose (e.g.,corn sugar) or other carbohydrates to glycerol, the processes disclosedin these publications provide a rapid, inexpensive and environmentallyresponsible source of 1,3-propanediol monomer.

The biologically-derived 1,3-propanediol, such as produced by theprocesses described and referenced above, contains carbon from theatmospheric carbon dioxide incorporated by plants, which compose thefeedstock for the production of the 1,3-propanediol. In this way, thebiologically-derived 1,3-propanediol preferred for use in the context ofthe present invention contains only renewable carbon, and not fossilfuel-based or petroleum-based carbon. The polytrimethylene ether glycoland deodorant compositions of the present invention utilizing thebiologically-derived 1,3-propanediol, therefore, have less impact on theenvironment as the 1,3-propanediol used in the compositions does notdeplete diminishing fossil fuels and, upon degradation, releases carbonback to the atmosphere for use by plants once again. Thus, thecompositions present invention can be characterized as more natural andhaving less environmental impact than similar compositions comprisingpetroleum based glycols.

The biologically-derived 1,3-propanediol, and polytrimethylene etherglycols, may be distinguished from similar compounds produced from apetrochemical source or from fossil fuel carbon by dual carbon-isotopicfinger printing. This method usefully distinguishes chemically-identicalmaterials, and apportions carbon in the copolymer by source (andpossibly year) of growth of the biospheric (plant) component. Theisotopes, ¹⁴C and ¹³C, bring complementary information to this problem.The radiocarbon dating isotope (¹⁴C), with its nuclear half life of 5730years, clearly allows one to apportion specimen carbon between fossil(“dead”) and biospheric (“alive”) feedstocks (Currie, L. A. “SourceApportionment of Atmospheric Particles,” Characterization ofEnvironmental Particles, J. Buffle and H. P. van Leeuwen, Eds., 1 ofVol. I of the IUPAC Environmental Analytical Chemistry Series (LewisPublishers, Inc) (1992) 3-74). The basic assumption in radiocarbondating is that the constancy of ¹⁴C concentration in the atmosphereleads to the constancy of ¹⁴C in living organisms. When dealing with anisolated sample, the age of a sample can be deduced approximately by therelationship

t=(−5730/0.693)In(A/A ₀)

where t=age, 5730 years is the half-life of radiocarbon, and A and A₀are the specific ¹⁴C activity of the sample and of the modern standard,respectively (Hsieh, Y., Soil Sci. Soc. Am J., 56, 460, (1992)).However, because of atmospheric nuclear testing since 1950 and theburning of fossil fuel since 1850, ¹⁴C has acquired a second,geochemical time characteristic. Its concentration in atmospheric CO₂,and hence in the living biosphere, approximately doubled at the peak ofnuclear testing, in the mid-1960s. It has since been gradually returningto the steady-state cosmogenic (atmospheric) baseline isotope rate(¹⁴C/¹²C) of ca. 1.2×10⁻¹², with an approximate relaxation “half-life”of 7-10 years. (This latter half-life must not be taken literally;rather, one must use the detailed atmospheric nuclear input/decayfunction to trace the variation of atmospheric and biospheric ¹⁴C sincethe onset of the nuclear age.) It is this latter biospheric ¹⁴C timecharacteristic that holds out the promise of annual dating of recentbiospheric carbon. ¹⁴C can be measured by accelerator mass spectrometry(AMS), with results given in units of “fraction of modern carbon”(f_(M)). f_(M) is defined by National Institute of Standards andTechnology (NIST) Standard Reference Materials (SRMs) 4990B and 4990C,known as oxalic acids standards HOxI and HOxII, respectively. Thefundamental definition relates to 0.95 times the ¹⁴C/¹²C isotope ratioHOxI (referenced to AD 1950). This is roughly equivalent todecay-corrected pre-Industrial Revolution wood. For the current livingbiosphere (plant material), f_(M≈)=1.1.

The stable carbon isotope ratio (¹³C/¹²C) provides a complementary routeto source discrimination and apportionment. The ¹³C/¹²C ratio in a givenbiosourced material is a consequence of the ¹³C/¹²C ratio in atmosphericcarbon dioxide at the time the carbon dioxide is fixed and also reflectsthe precise metabolic pathway. Regional variations also occur.Petroleum, C₃ plants (the broadleaf), C₄ plants (the grasses), andmarine carbonates all show significant differences in ¹³C/¹²C and thecorresponding δ ¹³C values. Furthermore, lipid matter of C₃ and C₄plants analyze differently than materials derived from the carbohydratecomponents of the same plants as a consequence of the metabolic pathway.Within the precision of measurement, ¹³C shows large variations due toisotopic fractionation effects, the most significant of which for theinstant invention is the photosynthetic mechanism. The major cause ofdifferences in the carbon isotope ratio in plants is closely associatedwith differences in the pathway of photosynthetic carbon metabolism inthe plants, particularly the reaction occurring during the primarycarboxylation, i.e., the initial fixation of atmospheric CO₂. Two largeclasses of vegetation are those that incorporate the “C₃” (orCalvin-Benson) photosynthetic cycle and those that incorporate the “C₄”(or Hatch-Slack) photosynthetic cycle. C₃ plants, such as hardwoods andconifers, are dominant in the temperate climate zones. In C₃ plants, theprimary CO₂ fixation or carboxylation reaction involves the enzymeribulose-1,5-diphosphate carboxylase and the first stable product is a3-carbon compound. C₄ plants, on the other hand, include such plants astropical grasses, corn and sugar cane. In C₄ plants, an additionalcarboxylation reaction involving another enzyme, phosphoenol-pyruvatecarboxylase, is the primary carboxylation reaction. The first stablecarbon compound is a 4-carbon acid, which is subsequentlydecarboxylated. The CO₂ thus released is refixed by the C₃ cycle.

Both C₄ and C₃ plants exhibit a range of ¹³C/¹²C isotopic ratios, buttypical values are ca. −10 to −14 per mil (C₄) and −21 to −26 per mil(C₃) (Weber et al., J. Agric. Food Chem., 45, 2942 (1997)). Coal andpetroleum fall generally in this latter range. The ¹³C measurement scalewas originally defined by a zero set by pee dee belemnite (PDB)limestone, where values are given in parts per thousand deviations fromthis material. The “δ¹³C” values are in parts per thousand (per mil),abbreviated % o, and are calculated as follows:

${\delta^{13}C} \equiv {\frac{{\left( {{\,^{13}C}/{\,^{12}C}} \right){sample}} - {\left( {{\,^{13}C}/{\,^{12}C}} \right){standard}}}{\left( {{\,^{13}C}/{\,^{12}C}} \right){standard}} \times 1000{\% \circ}}$

Since the PDB reference material (RM) has been exhausted, a series ofalternative RMs have been developed in cooperation with the IAEA, USGS,NIST, and other selected international isotope laboratories. Notationsfor the per mil deviations from PDB is δ¹³C. Measurements are made onCO₂ by high precision stable ratio mass spectrometry (IRMS) on molecularions of masses 44, 45 and 46.

Biologically-derived 1,3-propanediol, and compositions comprisingbiologically-derived 1,3-propanediol, therefore, may be completelydistinguished from their petrochemical derived counterparts on the basisof ¹⁴C (f_(M)) and dual carbon-isotopic finger-printing, indicating newcompositions of matter. The ability to distinguish these products isbeneficial in tracking these materials in commerce. For example,products comprising both “new” and “old” carbon isotope profiles may bedistinguished from products made only of “old” materials. Hence, theinstant materials may be followed in commerce on the basis of theirunique profile and for the purposes of defining competition, fordetermining shelf life, and especially for assessing environmentalimpact.

Preferably the 1,3-propanediol used as the reactant or as a component ofthe reactant will have a purity of greater than about 99%, and morepreferably greater than about 99.9%, by weight as determined by gaschromatographic analysis. Particularly preferred are the purified1,3-propanediols as disclosed in US20040260125A1, US20040225161A1 andUS20050069997A1, and polytrimethylene ether glycol made therefrom asdisclosed in US20050020805A1.

The purified 1,3-propanediol preferably has the followingcharacteristics:

(1) an ultraviolet absorption at 220 nm of less than about 0.200, and at250 nm of less than about 0.075, and at 275 nm of less than about 0.075;and/or

(2) a composition having CIELAB “b*” color value of less than about 0.15(ASTM D6290), and an absorbance at 270 nm of less than about 0.075;and/or

(3) a peroxide composition of less than about 10 ppm; and/or

(4) a concentration of total organic impurities (organic compounds otherthan 1,3-propanediol) of less than about 400 ppm, more preferably lessthan about 300 ppm, and still more preferably less than about 150 ppm,as measured by gas chromatography.

The starting material for making polytrimethylene ether glycol dependson the desired polytrimethylene ether glycol, availability of startingmaterials, catalysts, equipment, etc., and comprises “1,3-propanediolreactant.” By “1,3-propanediol reactant” is meant 1,3-propanediol, andoligomers and prepolymers of 1,3-propanediol preferably having a degreeof polymerization of 2 to 9, and mixtures thereof. In some instances, itmay be desirable to use up to 10% or more of low molecular weightoligomers where they are available. Thus, preferably the startingmaterial comprises 1,3-propanediol and the dimer and trimer thereof. Aparticularly preferred starting material comprises about 90% by weightor more 1,3-propanediol, and more preferably 99% by weight or more1,3-propanediol, based on the weight of the 1,3-propanediol reactant.

Polytrimethylene ether glycol can be made via a number of processesknown in the art, such as disclosed in U.S. Pat. No. 6,977,291 and U.S.Pat. No. 6,720,459. A preferred process is as set forth in previouslyincorporated US20050020805A1.

As indicated above, polytrimethylene ether glycol may contain lesseramounts of other polyalkylene ether repeating units in addition to thetrimethylene ether units. The monomers for use in preparingpolytrimethylene ether glycol can, therefore, contain up to 50% byweight (preferably about 20 wt % or less, more preferably about 10 wt %or less, and still more preferably about 2 wt % or less), of comonomerdiols in addition to the 1,3-propanediol reactant. Comonomer diols thatare suitable for use in the process include aliphatic diols, forexample, ethylene glycol, 1,6-hexanediol, 1,7-heptanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol,3,3,4,4,5,5-hexafluro-1,5-pentanediol,2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol;cycloaliphatic diols, for example, 1,4-cyclohexanediol,1,4-cyclohexanedimethanol and isosorbide; and polyhydroxy compounds, forexample, glycerol, trimethylolpropane, and pentaerythritol. A preferredgroup of comonomer diols is selected from the group consisting ofethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,2,2-diethyl-1,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol,C₆-C₁₀ diols (such as 1,6-hexanediol, 1,8-octanediol and1,10-decanediol) and isosorbide, and mixtures thereof. A particularlypreferred diol other than 1,3-propanediol is ethylene glycol, and C₆-C₁₀diols can be particularly useful as well.

One preferred polytrimethylene ether glycol containing comonomers ispoly(trimethylene-co-ethylene ether) glycol such as described inUS2004/0030095A1. Preferred poly(trimethylene-co-ethylene ether) glycolsare prepared by acid catalyzed polycondensation of from 50 to about 99mole % (preferably from about 60 to about 98 mole %, and more preferablyfrom about 70 to about 98 mole %) 1,3-propanediol and up to 50 to about1 mole % (preferably from about 40 to about 2 mole %, and morepreferably from about 30 to about 2 mole %) ethylene glycol.

Polytrimethylene ether glycols useful in practicing this invention cancontain small amounts of other repeat units, for example, from aliphaticor aromatic diacids or diesters, such as described in U.S. Pat. No.6,608,168. This type of polytrimethylene ether glycol can also be calleda “random polytrimethylene ether ester”, and can be prepared bypolycondensation of 1,3-propanediol reactant and about 10 to about 0.1mole % of aliphatic or aromatic diacid or esters thereof, such asterephthalic acid, isophthalic acid, bibenzoic acid, naphthalic acid,bis(p-carboxyphenyl)methane, 1,5-naphthalene dicarboxylic acid,2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid,4,4′-sulfonyl dibenzoic acid, p-(hydroxyethoxy)benzoic acid, andcombinations thereof, and dimethyl terephthalate, bibenzoate,isophthlate, naphthalate and phthalate; and combinations thereof. Ofthese, terephthalic acid, dimethyl terephthalate and dimethylisophthalate are preferred.

The polytrimethylene ether glycols preferred for use herein generallyhave a number average molecular weight from about 200 to about 3000, andpreferably from about 200 to about 2000. In embodiments where awater-soluble polytrimethylene ether glycol is used, the number averagemolecular weight is preferably less than about 1000, more preferablyfrom about 250 to about 950. The polytrimethylene ether glycolspreferred for use herein are typically polydisperse polymers having apolydispersity of preferably from about 1.0 to about 2.2, morepreferably from about 1.2 to about 2.0, and still more preferably fromabout 1.2 to about 1.8.

The polytrimethylene ether glycols for use in the present inventionpreferably have a color value of less than about 100 APHA, and morepreferably less than about 50 APHA.

Polytrimethylene ether glycol as described above should in general havelow acute oral toxicity, and not be a skin or eye irritant, or a skinsensitizer.

Mono- and Diesters of Polytrimethylene Ether Glycol (PO3G esters)

The PO3G esters used in the present invention can be described ascomprising one or more compounds of the formula (I):

wherein Q represents the residue of a polytrimethylene ether glycolafter abstraction of the hydroxyl groups, R₂ is H or R₃CO, and each ofR₁ and R₃ is individually a substituted or unsubstituted aromatic,saturated aliphatic, unsaturated aliphatic or cycloaliphatic organicgroup, containing from 6 to 40 carbon atoms.

PO3G esters are preferably prepared by polycondensation of hydroxylgroups-containing monomers (monomers containing 2 or more hydroxylgroups) predominantly comprising 1,3-propanediol to form a PO3G (asdisclosed in further detail below), followed by esterification with amonocarboxylic acid (or equivalent), as disclosed in previouslyincorporated U.S. application Ser. No. 11/593,954, filed Nov. 7, 2006,entitled “POLYTRIMETHYLENE ETHER GLYCOL ESTERS”.

The PO3G ester thus prepared is a composition preferably comprising fromabout 50 to 100 wt %, more preferably from about 75 to 100 wt %, diesterand from 0 to about 50 wt %, more preferably from 0 to about 25 wt %,monoester, based on the total weight of the esters. Preferably the mono-and diesters are esters of 2-ethylhexanoic acid, stearic acid, oleicacid, palmitic acid, linolenic acid and lauric acid. The deodorantcompositions comprise about 0.5 wt % to about 10 wt %, and preferablybetween about 1 wt % and 8 wt %, emulsifiers/solubilizers (e.gpoly(trimethylene ether)glycol ester (PO3G ester)).

The PO3G used for preparing the ester need not be the same as the PO3Gco-component of the base fluid stock.

When the vehicle comprises the PO3G esters as described above, it is notnecessary to add ethoxylated compounds. Thus, deodorant compositionswhich are substantially free of ethoxylated compounds (i.e., less thanabout 0.1 percent by weight of the total composition) can be produced.However, the presence of added ethoxylated compounds in deodorantcompositions or vehicles. does not render such vehicles or compositionsoutside the scope of the invention.

Functional Ingredients

In most embodiments, the deodorant products of the invention comprise,in addition to polytrimethylene ether glycol, some functional ingredientwhich provides benefit to the user's body. Such materials are in generalwell-known to those persons of ordinary skill in the relevant personalcare composition art, and may include moisturizing agents,anti-bacterials, and perfumes.

The functional ingredients (and other ingredients of the deodorantcompositions as described below) can be categorized by the benefit theyprovide or by their postulated mode of action. However, it is to beunderstood that the functional ingredients (and other ingredients)useful herein can in some instances provide more than one benefit oroperate via more than one mode of action. Therefore, classificationsherein are made for the sake of convenience and are not intended tolimit the active to that particular application or applications listed.

Examples of substances that may suitably be included in the deodorantproducts according to the present invention as functional ingredientsinclude the following:

(1) perfumes and fragrances, which give rise to an olfactory response inthe form of a fragrance, and deodorant perfumes which, in addition toproviding a fragrance response, can also reduce body malodor;

(2) skin coolants, such as menthol, menthyl acetate, menthyl pyrrolidonecarboxylate, N-ethyl-p-menthane-3-carboxamide and other derivatives ofmenthol, which give rise to a tactile response in the form of a coolingsensation on the skin;

(3) emollients, such as isopropylmyristate, mineral oils, vegetableoils, and glycerol/glycerine, which give rise to a tactile response inthe form of an increase in skin lubricity;

(4) deodorant ingredients other than perfumes, whose function is toreduce the level of or eliminate micro flora at the skin surface,especially those responsible for the development of body malodor,including precursors of deodorants;

(5) moisturizing agents, that keep the skin moist by either addingmoisture or preventing from evaporating from the skin;

(6) powders, pigments and colorants; and

(7) medicinal agents.

Further examples of skin benefit agents include abrasives; absorbents;aesthetic components such as opacifying agents and pearlescent aids suchas ethylene glycol distearate and TiO₂ coated mica; essential oils; skinsensates; cosmetic and drug astringents such as clove oil, menthol,camphor, eucalyptus oil, eugenol, menthyl lactate and witch hazeldistillate; anti-acne agents such as resorcinol, sulfur, salicylic acid,benzoyl peroxide, erythromycin and zinc; anti-caking agents;antimicrobial agents such as iodopropyl butylcarbamate; antioxidants;cosmetic biocides; external analgesics; pH modifiers such as citricacid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxideand sodium carbonate; skin soothing and/or healing agents such aspanthenol and derivatives like ethyl panthenol, aloe vera, pantothenicacid and its derivatives, allantoin; bisabolol and dipotassiumglycyrrhizinate; retinoids such as retinol palmitate); tocopherylnicotinate; skin treating agents; vitamins and derivatives thereof; andother similar materials.

Humectants have been described as agents that control the moistureexchange between the product and air, both in the container and on theskin. Humectants have also been described as compounds that preventdrying of skin or that increase the water content of the top layers ofskin (e.g., hygroscopic compounds).

Although polytrimethylene ether glycol is itself a useful humectant thathas a strong tendency to retain water and forms gel in the absence of agelling agent, it can also be used with other humectants or moisturizingagents, that: (a) facilitate hydration of the skin by inhibiting orpreventing loss of water; (b) absorb water from the atmosphere andhydrate the skin; (c) enhance the ability of the skin to absorb waterdirectly from the atmosphere; or (d) any combination thereof.Moisturizing agents also minimize or prevent the skin from drying andcracking.

Suitable moisturizing agents include hydrophobic agents, hydrophilicagents and combinations thereof. Examples of moisturizing agents areallantoin, glycerol, polyglycerylmethacrylate, panthenol, polyols,ceramide, borage oil (linoleic acid), tocopherol (Vitamin E), tocopherollinoleate, dimethicone, hyaluronic acid, sodium peroxylinecarbolic acid(sodium PCA), wheat protein (e.g., laurdimonium hydroxypropyl hydrolyzedwheat protein), hair keratin amino acids, panthenol; primrose oil; GLA 3and other fish oils that may include, for example, the omega-3 andomega-6 oils and/or linoleic acid; and flax seed oil, and mixturesthereof. Other moisturizing agents can also be used.

Other Ingredients

In the case of the present invention, the polytrimethylene ether glycoland water function as the vehicle (or a component of the vehicle), orone or both the polytrimethylene ether glycol and the active ingredientare generally dissolved, suspended or emulsified into a vehicle of thetypes discussed above.

A variety of other ingredients, in addition to those already mentioned,may also be present in the deodorant compositions of the presentinvention. Examples of such other ingredients include gelling agents,surfactants, emulsifiers, and preservatives. Also, salts of fatty acidssuch as sodium or potassium salts of stearic, palmitic, oleic orlinolenic acid, including mixtures thereof, can be present.

It is desirable that some or most of the ingredients in the deodorantcompositions disclosed herein be derived from renewable sources. Inpreferred embodiments, the compositions comprise greater than about 70percent renewably sourced ingredients, based on the total weight of thecomposition.

Cellulosic gums also can be used as additives in the compositions ofthis invention. For instance, US2003/0198616A1 describes a moisturizingskin gel wherein a water-soluble hydroxyalkylcellulose polymer typicallyperforms a dual function of gelling the composition and forming amoisture barrier to reduce transepidermal water loss. Preferredcellulosic gums include water-soluble hydroxyalkylcellulose polymerssuch as hydroxymethylcellulose, hydroxyethylcellulose andhydroxypropylcellulose. Other thickening agents which have been used inskin-contacting compounds, include acacia, agar, alginate, carrageenan,gum tragacanth, xanthan gum, collagen, carboxypolymethylene, glycerylmonostearate, polyvinylpyrrolidone and polyacrylamide.

Surfactants may be used in the deodorant compositions of the invention.Typical surfactants are disclosed in US2003/0007939A1.

A vast number of personal care products are oil-in-water emulsionscontaining a dispersion of oil droplets in a continuous aqueous medium.Surfactants or emulsifiers are generally used to aid emulsificationprocess of oil in water and to stabilize the thus formed emulsionagainst physical degradation processes. They are compounds that havehydrophobic and hydrophilic portions that act to reduce the surfacetension of the aqueous solutions they are dissolved in. Althoughpolytrimethylene ether glycol is easily dispersible in a continuousaqueous medium with out adding any emulsifier or surfactant, additionalemulsifiers may be used in many preferred embodiments of the invention.Most emulsifiers approved for cosmetic use can be used. Operableemulsifiers include nonionic, anionic, cationic, amphoteric orzwitterionic and blends thereof. Suitable emulsifiers are disclosed inU.S. Pat. No. 3,755,560 and U.S. Pat. No. 4,421,769. Examples arepolyethylene glycol 20, sorbitan monolaurate (Polysorbate 20),polyethylene glycol 20 stearyl ether (Brij 78, Steareth 20),polyethylene glycol ether of lauryl alcohol (Laureth 23), polysorbate 80(Tween 80), and lecithin. However, most of these surfactants arepetroleum based, and it is preferred to replace with renewably sourcedmaterials such as polytrimethyene ether glycol laurate of the presentinvention. Other commonly used ingredients in personal care compositionsinclude preservatives, which may be selected from the many that areknown in the art and commercially available. Examples include benzylalcohol, methyl paraben, propyl paraben, DMDM hydantoin,methylchloroisothiaoline, methylisothiazolinone, imidazolidinyl ureaphenoxyethanol, sodium benzoate and benzoic acid. EDTA and salts thereofare often used to further enhance preservation.

The deodorant compositions as described herein comprise a carrier orvehicle composition in the range of about 10 wt % to about 95 wt % ofthe total deodorant composition, preferably between about 20 wt % and 90wt %. Of this vehicle composition, about 5 wt % to about 85 wt %,preferably about 10 to about 70 wt %, is poly(trimethylene ether)glycol(PO3G). The vehicle generally comprises water, alcohol such as ethanol,isopropanol, diol such as 1,3-propanediol, 1,2-propanediol, polyol suchas glycerin, sorbitol, xylitol, mannitol, maltitol and oils such asvegetable oils, or a combination thereof. It is desirable that at leastsome of such ingredients be derived from renewable sources.

As stated above, the deodorant compositions comprise about 0.5 wt % toabout 10 wt %, preferably about 1 wt % to about 8 wt %, of a solidifyingor gelling agent (e.g., sodium stearate). The deodorant compositionscomprise about 0.5 wt % to about 10 wt %, and preferably between about 1wt % and 8 wt %, emulsifiers/solubilizers (e.g poly(trimethyleneether)glycol ester (PO3G ester).

The deodorant compositions also generally comprise one or morefunctional additives, including fragrance, antibacterial agents (e.g.IRGASAN) and the like. Generally, fragrances will be included in amountsbetween about 0.1 wt % to about 3 wt %, and preferably between about 0.3wt % and about 2.5 wt %. Fragrances can be selected from, for example,essential oils such as rosewood, lavender, lemon, lime, mandarin. rose,coriander, cypress, petitgrain, and pine. Antibacterial agents will beadded in amounts between about 0.1 wt % and 1.5 wt %, preferably betweenabout 0.2 wt % and 1.5 wt %. Examples of suitable antibacterial agentsinclude Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), andCHLORACEL® sodium aluminum chlorhydroxy lactate (Reheis, Inc., BerkeleyHeights, N.J.)

The deodorant compositions of this invention are readily prepared by useof conventional formulation and mixing techniques. Methods of makingseveral personal care compositions using polytrimethylene ether glycolare described in the examples, which are exemplary only and not intendedto be limiting.

Product Forms

Deodorant compositions or products are generally in the form of solid orgel sticks, creams, lotions, sprays etc. The compositions, thus, may bemade into a wide variety of product types. These include but are notlimited to, lotions, creams, gels, sticks, sprays, etc.

Most often deodorant products contain an active ingredient incorporatedin a delivery vehicle. The desired effect of a deodorant product isachieved either by the deodorant active ingredients or by the vehicleitself at the site of application, in most cases on the skin or hair.With the aid of the vehicle, i.e. the vehicle acting as a carrier, theactive ingredient is delivered to the application site where the desiredeffect is to be achieved.

The major types of deodorant vehicles most frequently fall into thefollowing categories: (a) solutions; (b) emulsions, both oil-in-waterand water-in-oil; and including lotions and creams; (c) suspensions; (d)gels; and (e) solids and semi-solids including stick products. Deodorantproducts in some vehicles, including liquids, gels, suspensions andemulsions, can be provided for application via roll-on applicator, asknown in the art. A discussion of personal care and cosmetic vehicles isfound in the previously incorporated Handbook of Cosmetic Science andTechnology, Second Edition, edited by M Paye, A. O. Barel and H. I.Maibach, pages 99-123 (2005).

Solutions Generally solutions used in personal care products are eitherbased on aqueous or aqueous alcoholic media, or on inert oily materials.Most organic solvents are not suitable because of their local orsystemic toxicity, which causes skin irritation or permeation into thebody. Examples of solvents, in addition to water, that are frequentlyused in personal care compositions are polypropylene glycol,polyethylene glycol, ethanol, glycerol, ethylene glycol,1,2,4-butanetriol, 1,2,6-hexanetriol, ethanol, isopropanol, butanetriol,sorbitol esters, butanediol, butylene glycol, hexylene glycol,methylpropanediol, pyrrolidone, N-methyl pyrrolidone, dimethylsulfoxide, dimethyl sulfone and similar solvents and mixtures thereof.Topical formulations containing such solvents are described in, forexample, US2004/0105873A1.

Preferred are aqueous solutions. Polytrimethylene ether glycols suitablefor aqueous solutions are either a homopolymer having molecular weight(Mn) of less than about 1000, or a water-soluble copolymer such aspolytrimethylene-ethylene ether glycol having molecular weight of lessthan about 3000. Preferred solutions will generally comprise loweramounts of polytrimethylene ether glycol, typically from about 0.1 toabout 10 wt % on the weight of the deodorant composition. Deodorantproducts are often formulated as solutions.

Gels

A “gel” in accordance with the present invention is a colloid in whichthe disperse phase has combined with the continuous phase to produce aviscous, jelly-like product.

Gels in accordance with the present invention can be aqueous ornon-aqueous. The gels will typically comprise a vehicle comprising, inaddition to the polytrimethylene glycol, a gelling agent such asdescribed above. The vehicle of the gels will also typically comprise asolvent.

A preferred deodorant composition in accordance with this aspect of thepresent invention comprises an effective amount of at least one activepersonal care ingredient in a vehicle, wherein the vehicle is a gelcomprising a gelling agent and from about 10 to about 70% by weight,based on the weight of the composition, of polytrimethylene etherglycol. Preferably, the vehicle comprises from about 30 to about 95% byweight, and more preferably from about 40 to about 80% by weight, basedon the weight of the composition, of polytrimethylene ether glycol. Thevehicle also preferably comprises a solvent, more preferably water.Deodorant compositions can be in gel form.

Polytrimethylene Ether Glycol/Water Gel

In one preferred embodiment, however, the gel is an aqueous gelcomprising water and lower molecular weight polytrimethylene etherglycol, where the polytrimethylene glycol functions as the gellingagent, and is preferably the sole gelling agent. In this embodiment, thegel is preferably non-flowable at ambient temperature (e.g., at about25° C. or below), and becomes a flowable liquid at a temperature ofabout 35° C. or higher and/or becomes a flowable liquid upon contactwith human or animal skin.

The gelation behavior of polytrimethylene ether glycol in thisembodiment is sensitive to molecular weight, comonomer amount and waterlevel. Depending on the polymer molecular weight and its concentration,when added to water and mixed it can form an emulsion or a homogenoussolution. Preferably, the polytrimethylene ether glycol should have amolecular weight (Mn) of less than about 1000, and should have acomonomer content of less than about 10 mole %. Preferably, thepolytrimethylene ether glycol is substantially a homopolymer of1,3-propanediol.

These gel compositions are easily prepared by adding polytrimethyleneether glycol directly into water at ambient temperature. The order ofaddition, polymer to water or water to polymer, is not critical. Noheating is required. The aqueous mixtures turn from a flowable fluidstate to a non-flowable gel or creamy state within a few minutes. Whenthe resulting gels are heated to a temperature above about 35° C., theyreturn to their original flowable state but are able to gel again uponcooling. Thus, in use, the gels become a liquid upon contact with humanor animal skin. As a result of this unique behavior of polytrimethyleneether glycol in water media, these lower molecular weightpolytrimethylene ether glycols possess a unique combination ofproperties and can be used as a lubricant, surfactant, humectant,moisturizer and emollient.

Any other ingredients added to this gel composition, such as an activedeodorant ingredient, are preferably added after gel formation.

This gelling behavior of the polytrimethylene ether glycol in aqueoussystems is unusual in comparison, for example, to certain ethylene oxideand propylene oxide block copolymers show gelation behavior in water athigh temperature but water-solubility at lower temperatures. Forexample, previously incorporated U.S. Pat. No. 5,256,396 discloses acomposition comprising water and a water soluble, non-ionic blockcopolymer of ethylene oxide and propylene oxide. This composition isflowable at or below ambient temperature, but upon contact with the warmsurface of an animal quickly forms a non-flowable gel. Thepolytrimethylene ether glycols exhibit the opposite behavior, forming anon-flowable gel at room temperature and turning into a flowable liquidupon contact with the warm surface of a human body.

The retention of water by polytrimethylene ether glycol by gel formationallows it to serve as an excellent moisturizing vehicle. This embodimentof the aqueous gel composition of the present invention is easily washedoff with water from the substrate such as the skin or face. Agents suchas ethylene/acrylic acid copolymers may be added to the compositions ofthe present invention to enhance their resistance to being washed off,if desired.

Emulsions

Emulsions are widely used as personal care vehicles. By “emulsion” ismeant a stable mixture of two or more immiscible liquids held insuspension by small percentages of substances called emulsifiers, whichmay be nonionic, anionic, cationic or zwitterionic. In the case ofoil-in-water emulsions, the oil phase is the internal or dispersedphase, and the water phase is the external (continuous) or carrierphase. In the case of water-in-oil emulsions, the water phase is theinternal or dispersed phase, and the oil phase water is the external(continuous) or carrier phase.

If emulsions are liquid (flowable at ambient temperature), they aregenerally referred to as lotions. Creams are emulsions that occur insubstantially non-flowable form (at ambient temperature). Generallycreams do not flow through orifices under gravity because of theirheavier consistency when compared to lotions. The consistency, orviscosity, of emulsions depends on several factors, including the ratioof internal to external phase, type of oil phase, and presence orabsence of thickening agents in the continuous phase.

Two phase emulsion skin care preparations, such as lotions and creams,of the oil-in-water type and water-in-oil type are well-known in thecosmetic art and are useful in the subject invention. Triphase emulsioncompositions, such as the water-in-oil-in-water type, as disclosed inU.S. Pat. No. 4,254,105, are also useful in the subject invention. Ingeneral, such triphase emulsions contain water, emollients andemulsifiers as essential ingredients. Oils useful in both types ofemulsions, and also for solvents in solvent-based vehicles in general,include hydrocarbon oils and waxes (e.g., petrolatum, mineral oil,micro-crystalline waxes, polyalkenes, paraffins, cerasin, ozokerite,polyethylene, perhydrosqualene, poly alpha olefins, hydrogenatedpolyisobutenes and combinations thereof). Preferred are fatty acidderivatives, cholesterol, cholesterol derivatives, diglycerides andtriglycerides (e.g., castor oil, soy bean oil, derivatized soybean oilssuch as maleated soy bean oil, safflower oil, cotton seed oil, corn oil,walnut oil, peanut oil, olive oil, cod liver oil, almond oil, avocadooil, palm oil, sesame oil, vegetable oils and vegetable oil derivatives,sunflower seed oil, coconut oil and derivatized coconut oil, cottonseedoil and derivatized cottonseed oil, jojoba oil, cocoa butter andcombinations thereof, as well as any of the aforementioned oils thathave been partially or fully hydrogenated), acetoglyceride esters (e.g.,acetylated monoglycerides), alkyl esters, alkenyl esters (e.g., oleylmyristate, oleyl stearate, oleyl oleate, and combinations thereof),lanolin and its derivatives (e.g., lanolin, lanolin oil, lanolin wax,lanolin alcohols, lanolin fatty acids, isopropyl lanolate, acetylatedlanolin, acetylated lanolin alcohols, lanolin alcohol linoleate, lanolinalcohol ricinoleate, hydroxylated lanolin, hydrogenated lanolin andcombinations thereof), wax esters (e.g., beeswax and beeswaxderivatives, spermaceti, myristyl myristate, stearyl stearate andcombinations thereof), sterols and phospholipids, and combinationsthereof. Examples of alkyl esters include isopropyl esters of fattyacids and long chain esters of long chain fatty acids, e.g., SEFA(sucrose esters of fatty acids), pentaerythritol esters, aromatic mono,di or triesters, cetyl ricinoleate, isopropyl palmitate, isopropylmyristate, cetyl ricinoleate and stearyl ricinoleate. Other examplesinclude hexyl laurate, isohexyl laurate, isohexyl palmitate, decyloleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropylisostearate, diisopropyl adipate, diisohexyl adipate, dihexyldecyladipate, diisopropyl sebacate, acyl isononanoate lauryl lactate,myristyl lactate, cetyl lactate, and combinations thereof. Still othersuitable oils include milk triglycerides (e.g., hydroxylated milkglyceride) and polyol fatty acid polyesters. Also useful are vegetablewaxes such as carnauba and candelilla waxes; sterols such ascholesterol, cholesterol fatty acid esters; and phospholipids such aslecithin and derivatives, sphingo lipids, ceramides, glycosphingolipids, and combinations thereof.

Suspensions

Still another aspect of the invention is a deodorant compositioncomprising a suspension. Suspensions consist of solid particlesdispersed in a liquid or semi-solid medium. Sedimentation during storageis minimized by reducing particle size and/or by increasing theviscosity of the carrier phase. Typical uses of suspensions areessentially the same as those listed above for oil-in-water andwater-in-oil emulsions.

Preferred suspensions comprise an effective amount of at least one solidactive deodorant ingredient in a vehicle comprising from about 60 toabout 90% by weight of polytrimethylene ether glycol, based on theweight of the deodorant composition. In one preferred embodiment, thevehicle comprises a solution of the polytrimethylene ether glycol and/orpoltyrimethylene ether glycol ester in a solvent. In a preferredembodiment, the composition is a lotion or a cream.

Solids

Yet another aspect of the invention relates to a personal carecomposition comprising an effective amount of at least one activepersonal care ingredient, a solidifying agent, and from about 10 toabout 90% by weight of polytrimethylene ether glycol based on the weightof the deodorant composition, wherein the composition is in the form ofa solid or semi-solid at ambient temperature (e.g., 25° C. and below).Preferably, the composition comprises from about 10 to about 80% byweight, more preferably from about 20 to about 70% by weight,polytrimethylene ether glycol.

Solid delivery vehicles are generally cast in an elongated form assticks. By rubbing the sticks onto the skin a variety of personal careingredients can be delivered. Examples include deodorant sticks. Thereare several ways of achieving solid stick properties, such as mixturesof waxes and oils and solutions based on aqueous, propylene glycoland/or alcohol mixtures solidified usually by sodium stearate;.Preferably, the solidifying agent is selected from the group consistingof a wax and sodium stearate. In preferred embodiments, the compositionsdescribed herein are substantially free from silicone-containingmaterials. “Substantially free” as used herein means less than about 0.1weight percent silicone of the total deodorant composition.

Solid personal care products of the invention may also be finely dividedand used in the form of powders.

Other Forms

It should be noted that most of the liquid vehicles described above canbe in the form of foams, which are dispersions of gas in the liquidphase. The gas globules may be of any size, from colloidal tomacroscopic, as in soap bubbles. Typical liquid foams are those used inshaving creams, etc.

Liquid or solid vehicle systems can also be applied as aerosols. By“aerosol” is meant a suspension of liquid or solid particles in a gas,the particles often being in the colloidal size range. Included are finesprays (deodorants, etc.). Suspensions of various kinds are prepared byplacing the components, together with a compressed gas, in a container(bomb). The pressure of the gas causes the mixture to be released as afine spray (aerosol) when a valve is opened. Examples are perfumes,deodorants, shaving cream, and the like. The propellant gas may be, forexample, a hydrocarbon (propane, isobutene), a chlorofluorocarbon,carbon dioxide or nitrous oxide.

EXAMPLES

Unless otherwise specified, the chemicals and reagents used in theexamples below were used as obtained from Sigma-Aldrich Co., St. Louis,Mo.

ZEMEA™ 1,3-propanediol is available from DuPont Tate & Lyle BioProducts, Wilmington, Del.

IRGASAN™ is Ciba Specialty Chemical's brand name for triclosan.

The fragrance used was Lavender French Essential Oil from New DirectionsAromatics, Inc., Toronto, Calif.

As used herein PEG means polyethylene glycol.

Water used in the examples below was distilled/deionized water.

Example 1 Synthesis of poly(trimethylene ether) glycol (PO3GHomopolymer)

A 22-L, 4-necked, round-bottomed flask, equipped with a nitrogen inlet,and a distillation head was charged with 11877 g of 1,3-propanediol. Theliquid was sparged with nitrogen at a rate of 10 L/min. and mechanicalstirring (using a stirring magnet driven by a magnetic stirrer below theflask) was done for about 15 min. After 15 min., 108 g of sulfuric acidwas slowly added drop-wise from a separatory funnel through one of theports over a period of at least 5 minutes. When this was finished, 15 gof 1,3-propanediol (PDO) was added to the separatory funnel and swirledto remove any residual sulfuric acid. This was added to the flask. Themixture was stirred and sparged as above and heated to 160° C. The waterof reaction was removed by distillation and was collected continuouslyduring the polymerization reaction. The reaction was continued for 14hours, after which it was allowed to cool (while stirring and spargingwere maintained) to 45° C.

The crude material was hydrolyzed as follows. The crude polymer wasadded to a 22-L, 5-necked, round-bottom flask, (equipped with acondenser and a mechanical mixer) along with an equal volume ofdistilled water. This mixture was stirred mechanically, sparged withnitrogen at a rate of about 150 mL/min. and heated to 100° C. It wasallowed to reflux for 4 hours after which the heat was turned off andthe mixture allowed to cool to 45° C. The stirring was discontinued andthe sparging reduced to a minimum. Phase separation occurred duringcooling. The aqueous phase water was removed and discarded. A volume ofdistilled water equal to the initial amount was added to the wet polymerremaining in the flask. Mixing, sparging and heating to 100° C. was doneagain for 1 hour after which the heat was turned off and the materialallowed to cool as before. The aqueous phase was removed and discarded.

The residual sulfuric acid was determined by titration and neutralizedwith an excess of calcium hydroxide. The polymer was dried under reducedpressure at 90° C. for 3 hours and then filtered through a Whatmanfilter paper precoated with a CEL-PURE C-65 filter aid. The resultingPO3G had a number average molecular weight of 500. A 200 ppm of BHT, anantioxidant was added to this polymer.

Example 2 Synthesis of poly(trimethylene-ethylene ether) glycolcopolymer

The above procedure described was repeated except for variation in theamounts of 1,3-propanediol (8811.2 g), 1,2-ethanediol (3080.8 g) andsulfuric acid (108 g) and the reaction time to 25 hours to obtain apoly(trimethylene-ethylene ether) glycol copolymer having a numberaverage molecular weight (Mn) of 890. A 200 ppm of BHT, an antioxidantwas added to this polymer.

Example 3 Synthesis of a 2-ethylhexanoate ester of polytrimethyleneether glycol

1,3-propanediol, 125 g was charged into a 500 mL flask fitted with astirrer, a condenser and an inlet for nitrogen. The liquid in the flaskwas flushed with dry nitrogen and 0.62 g of concentrated sulfuric acidwas added. The reaction temperature was raised to 170 ° C. and thereaction was allowed to proceed at 170° C. for 160 min. Then thetemperature was raised to 180° C. and held at 180° C. for 3 hours.

The reaction mixture was cooled to 110° C. and 70.95 g of2-ethylhexanoic acid (99%) was added. The reaction temperature was thenraised to 120° C. under nitrogen flow with continuous agitation at 180rpm and maintained at that temperature for 4 h. Then heating was stoppedand the product was allowed to cool to room temperature.

The 25 g of obtained product was mixed with 100 g of 1 wt % sodiumhydroxide solution, the mixture was thoroughly agitated and transferredto separating funnel. The aqueous layer was removed, 100 mL of water wasadded to product, thoroughly agitated and the aqueous layer was removed.The later step was repeated one more time. The product was dried at 90°C. using a rotovap. The product had a molecular weight of 385. Theobtained product was used in formulations in the Examples below.

Example 4 Synthesis of a laurate ester of polytrimethylene ether glycol

1,3-propanediol, 1504.5 g was charged into a 5 L flask fitted with astirrer, a condenser and an inlet for nitrogen. The liquid in the flaskwas flushed with dry nitrogen and heated to 170° C. After temperaturereached to 170° C., 7.8 g of concentrated sulfuric acid was added. Thereaction was allowed to continue for 3 h. The reaction temperature wasraised to 180° C. and the reaction was allowed to proceed 2 h 20 min.

305 g of obtained product was mixed with 400 g of lauric acid and 3.5 gof concentrated sulfuric acid in a 2 L flask fitted with a stirrer, acondenser and an inlet for nitrogen. The reaction temperature was raisedto 140° C. Then reaction was continued for 15 min at 140° C., 55 min at150° C. and 45 min at 165° C. Then the product was cooled.

450 g of obtained product was mixed with 955 g of 5 wt % sodiumcarbonate solution, and heated to 70° C. while stirring under nitrogenflow. After 30 min., the product was transferred to a separating funnel.The aqueous layer was removed. The product was dried at 90° C. using arotovap. The product had a molecular weight of 640. The obtained productwas used in formulations in the Examples below.

Deodorants with Polytrimethylene ether glycol of Example 1

The deodorant formulations described in the examples below consist offunctional ingredients (IRGASAN and Fragrance), a vehiclepolytrimethylene ether glycol (PO3G) and water, and other ingredientssuch as PEG monolaurate (solubilizer) and sodium stearate (solidifyingagent).

Stability of the deodorants made in the examples below was determined byvisual inspection. Stable formulations did not appreciably soften,expand or shrink at the temperatures listed with each example for atleast 30 days. Stability can also be determined by thermal analysistechniques, e.g., differential scanning calorimetry.

Example 5-6

Sodium stearate, Polytrimethylene ether glycol, PEG monolaurate, andwater were charged into a 250 mL flask fitted with a stirrer andblended. The blended mixture was heated to 90° C. while stirring at 180rpm. After the solids were completely melted and a clear solution wasformed, the temperature was reduced to 80° C. and triclosan was added.After 10 min the fragrance was added. Heating was stopped and theproduct was transferred into a container while cooling. The transferredproduct was allowed to cool to room temperature. The product of example5 was stable at 45° C. and the product of example 6 was stable at 40° C.

Ingredients Example 5 Example 6 Sodium stearate, % 6.5 10Poly(trimethylene ether) glycol, % 60 40 PEG monolaurate, % 2.0 2.0Water, % 31.0 47.5 IRGASAN ™ Triclosan, % 0.2 0.2 Fragrance, % 0.3 0.3

Example 7

6.5 g of sodium stearate, 30 g of poly(trimethylene ether) glycol, 30 gof ZEMEA™, 2.0 g of PEG monolaurate, and 31.0 g of water were chargedinto a 250 mL flask fitted with a stirrer and blended. The blendedmixture was heated to 90° C. while stirring at 180 rpm. After the solidswere completely melted and a clear solution was formed, the temperaturewas reduced to 80° C. and 0.2 g of triclosan was added. After 10 minfragrance was added. Heating was stopped and the product was transferredinto a container while cooling. The transferred product was allowed tocool to room temperature. The product was stable at 45° C. The vehiclecomposition of this deodorant had 34.0 wt % of poly(trimethylene ether)glycol.

Ingredients Wt % Sodium stearate 6.5 Poly(trimethylene ether) glycol30.0 ZEMEA ™ 30.0 PEG monolaurate 2.0 Water 31.0 IRGASAN ™ Triclosan,0.2 Fragrance 0.3

Example 8

6.5 g of sodium stearate, 12 g of poly(trimethylene ether) glycol, 50 gof ZEMEA™, and 31.0 g of water were charged into a 250 mL flask fittedwith a stirrer and blended. The blended mixture was heated to 90° C.while stirring at 180 rpm. After solids were completely melted and aclear solution was formed, the temperature was reduced to 80° C. and 0.2g of triclosan was added. After 10 min fragrance was added. Heating wasstopped and the product was transferred into a container while cooling.The transferred product was allowed to cool to room temperature. Theproduct was stable at 45° C. The vehicle composition of this deodoranthad 12.9 wt % of poly(trimethylene ether) glycol.

Ingredients Wt % Sodium stearate 6.5 Poly(trimethylene ether) glycol12.0 ZEMEA ™ 50.0 Water 31.0 IRGASAN ™ Triclosan 0.2 Fragrance 0.3

Examples 9-11 Deodorants comprising Polytrimethylene ether glycolEster(s) (non-ethoxylated) Example 9

6.5 g of sodium stearate, 60.0 g of ZEMEA™, 2.0 g of poly(trimethyleneether) glycol ester (as made according to example 3 above), and 31.0 gof water were charged into a 250 mL flask fitted with a stirrer andblended. The blended mixture was heated to 90° C. while stirring at 180rpm. After solids were completely melted and a clear solution wasformed, the temperature was reduced to 80° C. and 0.2 g of triclosan wasadded. After 10 min fragrance was added. Heating was stopped and theproduct was transferred into container while cooling. The transferredproduct was allowed to cool to room temperature. The product was stableat 45° C. The deodorant had 2 wt % of poly(trimethylene ether) glycol2-ethylhexanoate.

Ingredients Wt % Sodium stearate 6.5 ZEMEA ™ 60 Poly(trimethylene ether)glycol 2.0 2-ethylhexanoate Water 31.0 IRGASAN ™ Triclosan 0.2 Fragrance0.3

Example 10

6.5 g of sodium stearate, 50.0 g of ZEMEA™, 10.0 g of poly(trimethyleneether) glycol, 2.0 g of poly(trimethylene ether) glycol 2-ethylhexanoateof example 3, and 31.0 g of water were charged into a 250 mL flaskfitted with a stirrer and blended. The blended mixture was heated to 90°C. while stirring at 180 rpm. After the solids were completely meltedand a clear solution was formed, the temperature was reduced to 80° C.and 0.2 g of triclosan was added. After 10 min fragrance was added.Heating was stopped and the product was transferred into a containerwhile cooling. The transferred product was allowed to cool to roomtemperature. The product was stable at 45° C. The vehicle composition ofthis deodorant has 11 wt % of poly(trimethylene ether) glycol and thedeodorant composition had 2 wt % of poly(trimethylene ether) glycol2-ethylhexanoate.

Ingredients Wt % Sodium stearate 6.5 ZEMEA ™ 50.0 Poly(trimethyleneether) glycol 10.0 Poly(trimethylene ether) glycol 2.0 2-ethylhexanoateWater 31.0 IRGASAN ™ Triclosan 0.2 Fragrance 0.3

Example 11

6.5 g of sodium stearate, 50.0 g of ZEMEA™, 10.0 g of poly(trimethyleneether) glycol of example 1, 2.0 g of poly(trimethylene ether) glycollaurate of example 4, and 31.0 g of water were charged into a 250 mLflask fitted with a stirrer and blended. The blended mixture was heatedto 90° C. while stirring at 180 rpm. After the solids were completelymelted and a clear solution was formed, the temperature was reduced to80° C. and 0.2 g of triclosan was added. After 10 min fragrance wasadded. Heating was stopped and the product was transferred into acontainer while cooling. The transferred product was allowed to cool toroom temperature. The product was stable at 45° C. The vehiclecomposition of this deodorant has 11 wt % of poly(trimethylene ether)glycol and the deodorant has 2 wt % of poly(trimethylene ether) glycollaurate.

Ingredients Wt % Sodium stearate 6.5 ZEMEA ™ 50.0 Poly(trimethyleneether) glycol 10.0 Poly(trimethylene ether) glycol 2.0 laurate Water31.0 IRGASAN ™ Triclosan 0.2 Fragrance 0.3

Example 12

6.5 g of sodium stearate, 60.0 g of poly(trimethylene-ethylene ether)glycol copolymer of example 2, 2.0 g of PEG monolaurate, and 31.0 g ofwater were charged into a 250 mL flask fitted with a stirrer andblended. The blended mixture was heated to 90° C. while stirring at 180rpm. After the solids were completely melted and a clear solution wasformed, the temperature was reduced to 80° C. and 0.2 g of triclosan wasadded. After 10 min fragrance was added. Heating was stopped and theproduct was transferred into container while cooling. The transferredproduct was allowed to cool to room temperature. The product was stableat 45° C. The vehicle composition of this deodorant had 65.9 wt % ofpoly(trimethylene ether) glycol copolyol.

Ingredients Wt % Sodium stearate 6.5 Poly(trimethylene-ethylene 60.0ether) glycol PEG monolaurate 2.0 Water 31.0 IRGASAN ™ Triclosan 0.2Fragrance 0.3

1. A deodorant composition comprising an effective amount of at leastone active deodorant ingredient in a vehicle, wherein the vehiclecomprises polytrimethylene ether glycol.
 2. A deodorant compositionaccording to claim 1 wherein the vehicle further comprises one or morerenewably sourced materials selected from: water, ethanol, butanol,1,3-propanediol, glycerine, 1,2-propylene glycol, sorbitol, xylitol,mannitol, maltitol and vegetable oils.
 3. The deodorant composition ofclaim 1, wherein said vehicle comprises from about 5 to 85 percent byweight, based on the weight of the vehicle, of polytrimethylene etherglycol.
 4. The deodorant composition of claim 1, wherein said vehiclecomprises from about 10 to 70 percent by weight, based on the weight ofthe vehicle, of polytrimethylene ether glycol.
 5. The deodorantcomposition of claim 1, wherein the polytrimethylene ether glycol has anumber average molecular weight of 200 to
 3000. 6. The deodorantcomposition of claim 1, wherein said composition is substantially freeof silicone-containing materials.
 7. A deodorant composition comprisingpolytrimethylene ether glycol ester and at least one active deodorantingredient.
 8. The deodorant composition of claim 1, further comprisingpolytrimethylene ether glycol ester.
 9. The deodorant composition ofclaim 8, where in the composition comprises from 0.1 to 10% by weight,based on the total weight of the composition, of polytrimethylene etherglycol ester.
 10. The deodorant composition of claim 7 wherein saidcomposition is substantially free of ethoxylated materials.
 11. Thedeodorant composition of claim 1, wherein said composition furthercomprises one or more of (a) sodium or potassium salts of fatty acids;(b) fragrances (c) antibacterial agents; and (d) colorants.
 12. Thedeodorant composition of claim 1, comprising greater than about 70percent renewably sourced ingredients, based on the total weight of thecomposition.
 13. The deodorant composition of claim 2, wherein theamount of one or more renewably sourced materials is from about 15 to 95percent by weight, based on the weight of the vehicle.
 14. The deodorantcomposition of claim 11, further comprising one or more polytrimethyleneether glycols and/or polytrimethylene ether glycol ester(s).
 15. Thedeodorant composition of claim 13, wherein said composition issubstantially free of silicone-containing materials.
 16. The deodorantcomposition of claim 15, wherein said composition further comprises oneor more of: (a) sodium or potassium salts of fatty acids; (b) fragrances(c) antibacterial agents; and (d) colorants.
 17. The deodorantcomposition of claim 1 or 13 in a form selected from the groupconsisting of solid and gels sticks, creams, lotions, liquids andsprays.
 18. The deodorant composition of claim 13, comprising greaterthan about 70 percent renewably sourced ingredients, based on the totalweight of the composition.